Unsaturated esters of 2-chloroallyl alcohol



solvent. The reacted mixture is treated with suf- Patented Aug. 23, 1938I "'UNSATURATED ESTERS OF -2-CHLOROALLYL ALCOHOL Gerald H. Coleman andBartholdt C. Hadler, .Midland, Mich., assignors to The Dow ChemicalCompany, Midland, Mich, a corporation of 'Michigan No Drawing.Application October 23, 1937, Serial No. 170,647

8 Claims. (Cl. 260-469) at 105-10'l C. under 4 millimeters pressure andhaving a specific gravity of 1.253 at 20/4" 0., and a refractive index,

n,2= 1.530 Example 2 A mixture of 58.0 grams (0.50 mol.) of maleic acid,92.5 grams (1 mol.) of 2-chloroallyl alcohol, .and 5 grams of benzenesulphonic acid was heated at 83-91 C. for 6 hours. During the heatingbenzene was added drop-wise to facilitate the distillation of water fromthe mixture. The reacted mixture was dissolved in benzene and washedwith dilute aqueous sodium bicarbonate solution and water. Benzene wasremoved by distillation and the ester product fractionally distilled.There was obtained 80 grams per cent of the theoretical yield) ofdi-(Z-chlo'roallyl) maleate, a colorless liquid distilling at 155-160 C.under 5 millimeters pressure.

This invention concerns esters of 2-chloroallyl alcohol with unsaturatedcarboxylic acids; particularly esters having the general formula R-COCHz-C=CH2 1: wherein R is a hydrocarbon radical containing at leastone ethyienic linkage and n is an integer. All such esters are newcompounds useful as intermediates in the'preparation of other organiccompounds and as modifiers in the polymerization of vinyl compounds,particularly styrene.

The unsaturated esters of 2-chloroallyl alcohol may be prepared byesterifying 2-chloroallyl alcohol with an unsaturated carboxylic acid,e. g. acrylic acid, methacrylic acid, crotonic acid, sorbic acid,fumaric acid, citraconic acid, cinnamic aid, furoic acid, etc. Theesteriflcation may be carried out by heating a mixture of 2-chloroallylalcohol and approximately one chemical equivalent of an unsaturatedcarboxylic acid, together with a small proportion of a catalyst, e. g.approximately 0.01-0.04 molecular equivalents of a strong acid, such assulphuric or benzene sulphonic acid, at a temperature of approximately-120 C. Water is formed in the reaction and, if desired, awater-immiscible organic solvent, such as benzene or toluene, may beadded for the purpose of promoting the vaporization and removal of wateras an azeotropic mixture with the Example 3 A mixture of 86.0 grams (1mol.) of crotonic acid, 92.5 grams (1 mol.) of 2-chloroallyl alcohol,and 5 grams of sulphonic acid was heated at 96- 108 C. for 5 hours as inExample 1. The reacted mixture was dissolved in benzene andwashed withdilute aqueous sodium bicarbonate solution and water. Benzene wasremoved by distillation and the ester product fractionally distilled.There was obtained 131.5 grams (82 per cent of the theoretical yield) of2-chloroallyl crotonate, a colorless liquid distilling at 65-67 C. under4 millimeters pressure, having a specific gravity of 1.102 at 20/4 0.,and a refractive index,

Example 4 ficient alkali to neutralize the acid contained therein, afterwhich the ester product is separated by fractional distillation undervacuum.

The following examples illustrate a number of ways in which theprinciple of our invention may be employed, but are not to be construedas limiting the same:-

Example 1 A mixture of 112.0 grams (1 mol.) of furoic acid, 92.5 grams(1 mol.) of 2-chloroal1yl alcohol,- and 5 grams of benzene sulphonicacid was heated at -105 C. for 6% hours in a flask fitted with droppingfunneL condenser, and receiver arranged Washed and the Product recoveredas in mp e in such manner as to permit distillation of water There wasObtained glams (59 per cent from themixture. During the heating be ofthe theoretical yield) of 2-chloroallyl cinnawas added drop-wise tofacilitate the distillation mate, a colorless liquid distilling at153-155 c.

A mixture of 69 grams (0.47 mol.) of cinnamic acid, 43 grams (0.47 mol.)of 2-chloroallyl alcohol, and 2.5 grams of benzene sulphonic acid washeated at 93-l05 C. for8 hours as in Example 1. The reacted mixture wasdissolved in benzene,

of water. The reacted mixture was allowed to under 4 millimeterspressure, having a Spec fic c 1 dissolved in benzene and washed uncegravity Of at 20/4 C., and a refractive index, 250 cc. of a 5 per centaqueous sodium bicarbonate 2 5775 solution and once with 250 cc. ofwater. Benzene Example 5 was removed by distillation and the esterproduct distilled under vacuum. There was obtained 2-chloroallylfuroate, a colorless liquid distilling A mixture of 44.3 grams (0.25mol.) of betabenzoyl-acrylic acid, 23.1 grams (0.25 mol.) of

z-chloroallyl alcohol, and 2 grams of benzene sulphonlc acid was heatedat 85-88 C. for 4% hours as in Example 1. The reacted mixture wasdissolved in benzene, washed, and the product recovered as in Example 1.There was obtained 2-chloroallyl beta-benzoyLacrylate, a colorlessliquid which distills at approximately 175l85 C. under 4 millimeterspressure, and which polymerizes during distillation to a dark-brown,brittle solid, soluble in acetone, benzene, carbon tetrachloride andother organic solvents.

Other unsaturated esters of 2-chloroallyl alcohol may be prepared from2-chloroallyl alcohol and unsaturated carboxylic acids. For example,2-chloroallyl alcohol may be reacted with furylacrylic acid to producez-chloroallyl furylacrylate with oleic acid to produce z-chloroallyloleate; with allylacetic acid to produce 2-ch1oroallyl a1- lylacetate;with linoleic acid to produce 2-ch1oroallyl linoleate; withbeta-chloro-acrylic acid to produce 2-chloroallyl betachloroacrylate;etc.

Other modes of applying the principle of our invention may be employedinstead of those explained, change being made as regards the materialsemployed, provided the ingredients stated by any of the following claimsor the equivalent of such stated ingredients be employed.

We therefore particularly point out and distinctly claim as ourinvention:

1. An ester of 2-chloroally1 alcohol with an unsaturated carboxylicacid.

2. An unsaturatedcarboxylic acid ester of 2- chloroallyl alcohol havingthe general formula R-(CO-CHr-C=CH2 fl wherein R represents ahydrocarbon group containing at least one ethylenic linkage, and nrepresents an integer.

3. An unsaturated carboxylic acid ester of 2- chloroallyl alcohol havingthe general formula Cl Rc:0om 3=cm wherein R represents a hydrocarbongroup containing at least one ethylenic linkage.

4. An unsaturated carboxylic acid ester of 2- chloroallyl alcohol havingthe general formua c1 0 0 01 I ll b CHa=C-CHzO-CR "O-CH2-- =CH| whereinR represents a hydrocarbon group containing at least one ethyleniclinkage.

5. An unsaturated carboxylic acid ester of 2- chloroallyl alcohol havingthe general formula '7. 2-chloroallyl crotonate, a colorless liquiddistilling at 65-67 C. under 4 millimeters pressure,

and having a specific gravity of 1.102 at 20/4 0.,

and the formula 0 c1 CH:CH=CHC OCHz=CHz 8. Di-(Z-chloroallyl) maleate, acolorless liquid distilling at approximately 155-160 C. under 5millimeters pressure, and the formula GERALD H. COLEMAN. BARTHOLDT C.HADLER.

